WO2016158157A1

WO2016158157A1 - Novel episulfide compound and optical material composition containing same

Info

Publication number: WO2016158157A1
Application number: PCT/JP2016/056154
Authority: WO
Inventors: 慶彦西森; 嘉村　輝雄; 堀越　裕
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2015-03-31
Filing date: 2016-03-01
Publication date: 2016-10-06
Also published as: TW201641498A; KR20170066660A; EP3208268A1; CN107250125A; EP3208268B1; TWI632141B; JP6245408B2; KR20180061429A; US20170247351A1; JPWO2016158157A1; CN107250125B; EP3208268A4; KR102482153B1; BR112017011529A2; BR112017011529B1; US10065940B2

Abstract

According to the present invention, it is possible to provide an optical material composition that contains an episulfide compound represented by formula (1) and an episulfide compound represented by formula (2). According to this optical material composition, it is possible to suppress a reduction in the yield rate caused by molding defects, and possible to obtain an optical material having excellent dyeability. (In formula (1), m and p are each an integer between 0 and 4, and n and q are each an integer between 0 and 2.) (In formula (2), m is an integer between 0 and 4 and n is an integer between 0 and 2.)

Description

Novel episulfide compound and composition for optical material containing the same

The present invention relates to a novel episulfide compound and a composition for optical materials containing the same, and in particular, a novel episulfide compound suitably used for optical materials such as plastic lenses, prisms, optical fibers, information recording substrates, filters, and especially plastic lenses. And an optical material composition containing the same.

Plastic lenses are light and tough and easy to dye. The performance particularly required for the plastic lens is low specific gravity, high transparency and low yellowness, and high optical refractive index, high Abbe number, high heat resistance, high strength and the like. A high refractive index enables the lens to be thinned, and a high Abbe number reduces the chromatic aberration of the lens.
In recent years, many examples using organic compounds having sulfur atoms have been reported for the purpose of high refractive index and high Abbe number. Among them, it is known that a polyepisulfide compound having a sulfur atom has a good balance between the refractive index and the Abbe number (Patent Document 1). Since polyepisulfide compounds can react with various compounds, compositions with various compounds have been proposed to improve physical properties (Patent Documents 2 to 5).
However, lenses produced from episulfide compounds may be difficult to dye by methods commonly used in plastic lenses, and may not sufficiently meet the required characteristics of spectacle lenses where design is important. . In addition, with high-number lenses, the releasability is poor, so the lens may be missing at the time of demolding, or the releasability is too good to peel off from the mold during polymerization and the required surface accuracy may not be obtained. .

Japanese Patent Application Laid-Open No. 09-110979 Japanese Patent Laid-Open No. 10-298287 JP 2001-002783 A JP 2001-131257 A JP 2002-122701 A

An object of the present invention is to provide a composition for an optical material capable of suppressing a decrease in the yield rate due to defective release and an optical material excellent in dyeability.

As a result of intensive studies in view of such circumstances, the present inventors have obtained an episulfide compound represented by the following formula (1), an episulfide compound represented by the following formula (1), and the following formula (2). This problem was solved by the composition for optical materials containing the episulfide compound represented, and it came to this invention. That is, the present invention is as follows.
<1> An episulfide compound represented by the following formula (1).

(In the formula, m and p are integers of 0 to 4, and n and q are integers of 0 to 2.)
<2> An optical material composition comprising an episulfide compound represented by the formula (1) described in the above <1> and an episulfide compound represented by the following formula (2).

(In the formula, m represents an integer of 0 to 4, and n represents an integer of 0 to 2.)
<3> The composition for optical materials according to <2>, wherein the content of the episulfide compound represented by the formula (1) is 0.001 to 5.0% by mass.
<4> The composition for optical materials according to the above <2> or <3>, wherein the content of the episulfide compound represented by the formula (2) is 40 to 99.999% by mass.
<5> The composition for optical materials according to any one of <2> to <4>, further including polythiol.
<6> The composition for optical materials according to any one of <2> to <5>, further containing sulfur.
<7> The composition for optical materials according to <5> or <6>, further including polyisocyanate.
<8> The composition for optical materials according to any one of <2> to <7> above, and 0.0001% by mass to 10% by mass of a polymerization catalyst based on the total amount of the composition for optical materials. It is a polymerization curable composition.
<9> An optical material obtained by curing the composition for optical materials according to any one of <2> to <7> or the polymerization curable composition according to <8>.
<10> An optical lens including the optical material according to <9>.
<11> A step of adding 0.0001% by mass to 10% by mass of a polymerization catalyst with respect to the total amount of the composition for optical materials according to any one of the above <2> to <7>, and curing by polymerization. It is a manufacturing method of an optical material.
<12> The method for producing an optical material according to <11>, wherein the episulfide compound represented by the formula (2) and sulfur are partially polymerized in advance and then polymerized and cured.

According to the present invention, when an optical material having a high refractive index is produced, it is possible to obtain a composition for an optical material that is unlikely to cause defective release and that provides an optical material having excellent dyeability.

Hereinafter, the present invention will be described in detail.
The present invention is an optical material composition comprising an episulfide compound represented by the formula (1), and an episulfide compound represented by the formula (1) and a polymerizable compound. Examples of the polymerizable compound include an episulfide compound, a vinyl compound, a methacrylic compound, an acrylic compound, and an allyl compound, preferably an episulfide compound, and more preferably an episulfide compound represented by the formula (2).
The ratio of the episulfide compound represented by the formula (1) in the composition for optical materials of the present invention is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 3.0. % By mass, particularly preferably 0.01 to 1.0% by mass. If the episulfide compound represented by the formula (1) is less than 0.001% by mass, a sufficient effect may not be obtained, and if it exceeds 5.0% by mass, the releasability may be deteriorated. The proportion of the polymerizable compound in the composition for optical materials of the present invention is preferably 95.0 to 99.999% by mass, more preferably 97.0 to 99.995% by mass, and particularly The content is preferably 99.0 to 99.99% by mass. When the episulfide compound represented by the formula (2) is used as the polymerizable compound, the proportion of the episulfide compound represented by the formula (2) in the composition for optical materials is 40 to 99.999 mass%. It is preferably 50 to 99.995% by mass, particularly preferably 60 to 99.99% by mass.
Hereinafter, the episulfide compound represented by the formula (1) and the episulfide compound represented by the formula (2) will be described in detail.

The present invention is an episulfide compound represented by the formula (1), and the episulfide compound represented by the formula (1) is used in the composition for optical materials of the present invention. In the formula (1), preferably, m and p are integers of 0 to 2, n and q are integers of 0 or 1, more preferably m and p are 0 and n and q are 1, or n and q Is a compound in which n and q are 0. The episulfide compound represented by the formula (1) may be used alone or in combination of two or more.

Hereinafter, although the manufacturing method of the episulfide compound represented by Formula (1) of this invention is demonstrated, a manufacturing method is not specifically limited.
As a method for producing an episulfide compound represented by the formula (1) of the present invention, a compound represented by the following formula (3) is first obtained by reacting hydrogen sulfide or polythiol with an epihalohydrin compound. When obtaining a compound in which n and q are 0, or a compound in which m and p are 0, n and q are 1, the obtained compound represented by the formula (3) is obtained by using thiourea, thiocyanate, etc. To obtain a compound represented by the formula (4). In the case of producing a compound in which n and q are 0, a compound represented by the following formula (5) is obtained by reacting a compound represented by the formula (4) with an epihalohydrin compound, and then the obtained formula After the compound represented by (5) is reacted with an alkali to proceed the dehydrohalogenation reaction to obtain a compound represented by the following formula (6), it is further represented by the obtained formula (6). The compound is reacted with a thiating agent such as thiourea or thiocyanate to obtain an episulfide compound represented by the formula (1).
In the case of producing a compound in which m and p are 0, and n and q are 1, the compound represented by the formula (4) is reacted with 3-mercapto-1,2-propylene sulfide to represent the compound represented by the formula (1). An episulfide compound is obtained. As another production method, a compound represented by the formula (3) is reacted with an alkali to proceed a dehydrohalogenation reaction to obtain a compound represented by the following formula (7), and then with hydrogen sulfide. After obtaining the compound represented by the following formula (8) by the reaction, the compound represented by the following formula (8) is further reacted with a thiating agent such as thiourea and thiocyanate to formula (1) There is also a method for obtaining an episulfide compound represented by:

(In the formula, X represents a halogen atom, m represents an integer of 0 to 4, and n represents an integer of 0 to 2.)

(In the formula, X represents a halogen atom.)

(In the formula, m represents an integer of 0 to 4, and n represents an integer of 0 to 2.)

(In the formula, m and p are integers of 0 to 4, and n and q are integers of 0 to 2.)

It describes about the manufacturing method of the compound represented by Formula (3). By using the compound represented by the formula (7) instead of the epihalohydrin compound, the compound represented by the formula (8) can also be produced by the same method.
The compound represented by Formula (3) is obtained by reaction of hydrogen sulfide or a polythiol compound with an epihalohydrin compound. Examples of polythiol compounds are methanedithiol, 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, and bis (2-mercaptoethyl) sulfide. Of the hydrogen sulfide or polythiol compounds, hydrogen sulfide, 1,2-dimercaptoethane, and bis (2-mercaptoethyl) sulfide are preferable, and hydrogen sulfide is most preferable. Examples of the epihalohydrin compound include epichlorohydrin and epibromohydrin, with epichlorohydrin being preferred.
In the reaction of epihalohydrin with hydrogen sulfide or a polythiol compound, a catalyst is preferably used. Examples of the catalyst include inorganic acid, organic acid, Lewis acid, silicic acid, boric acid, quaternary ammonium salt, inorganic base, organic base and the like. Preferred are organic acids, quaternary ammonium salts, and inorganic bases, and more preferred are quaternary ammonium salts and inorganic bases. Specific examples include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium acetate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium acetate, tetrahexylammonium. Examples include chloride, tetrahexylammonium bromide, tetrahexylammonium acetate, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium acetate, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide. Of these, sodium hydroxide, potassium hydroxide, and calcium hydroxide are preferred.

The amount of the catalyst added is not particularly limited as long as the reaction is allowed to proceed. However, it is preferably used in an amount of 0.00001 to 0.5 mol, more preferably 0.001 to 0.1 mol, relative to 1 mol of epihalohydrin. . If the amount is less than 0.00001 mol, the reaction does not proceed or becomes too slow, which is not preferable.
The ratio of epihalohydrin to hydrogen sulfide or polythiol compound is not particularly limited as long as the reaction proceeds. Preferably, the molar ratio of epihalohydrin to H of thiol group (SH group) or hydrogen sulfide of polythiol compound is 0.3. -4, more preferably 0.4-3, still more preferably 0.5-2. If it is less than 0.3 or exceeds 4, the surplus of unreacted raw materials increases, which is not economically preferable.

A solvent may or may not be used, but when used, water, alcohols, ethers, ketones, aromatic hydrocarbons, halogenated hydrocarbons and the like are used. Specific examples include water, methanol, ethanol, propanol, isopropanol, diethyl ether, tetrahydrofuran, dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, acetone, benzene, toluene, xylene, dichloroethane, chloroform, chlorobenzene and the like. Is mentioned. Among these, water, methanol, and toluene are preferable, and water and methanol are particularly preferable.
The reaction temperature is not particularly limited as long as the reaction is allowed to proceed, but is preferably −10 ° C. to 80 ° C., more preferably 0 ° C. to 50 ° C., and further preferably 0 ° C. to 40 ° C. The reaction time is not particularly limited, but is usually 20 hours or less. If it is less than −10 ° C., it is not preferable because the reaction does not proceed or becomes too slow.

It describes about the manufacturing method of the compound represented by Formula (4) from the compound represented by Formula (3).
A compound represented by the formula (4) is obtained by reacting a compound represented by the formula (3) with a thiating agent such as thiourea or thiocyanate. Preferred thiating agents are thiurea, sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, and a particularly preferred compound is thiourea. As the thialating agent, the number of moles corresponding to the halogen of the compound represented by the formula (3), that is, the theoretical amount is used. If importance is attached to the reaction rate and purity, the theoretical amount is 2.5 times the theoretical amount. Use moles. The molar amount is preferably 1.3 times the theoretical amount to 2.0 times the theoretical amount, more preferably 1.5 times the theoretical amount to 2.0 times the theoretical amount.
The solvent is not particularly limited as long as it dissolves the chelating agent, the compound represented by the formula (4), and the compound represented by the formula (3). Specific examples include alcohols such as methanol and ethanol. , Ethers such as diethyl ether, tetrahydrofuran and dioxane, hydroxy ethers such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, aromatic hydrocarbons such as benzene and toluene, halogenated carbonization such as dichloromethane, chloroform and chlorobenzene Examples include hydrogen and water. Preferred are alcohols, aromatic hydrocarbons, and water, and more preferred are methanol and toluene. These may be used alone or in combination.
The reaction temperature is not particularly limited as long as the reaction proceeds. Usually, the reaction is carried out at 10 ° C to 50 ° C. When the temperature is lower than 10 ° C., in addition to the decrease in the reaction rate, the thiating agent is insufficiently dissolved and the reaction does not proceed sufficiently. When the temperature exceeds 50 ° C., the formation of the polymer becomes remarkable.

It is preferable to add an acid or acid anhydride or an ammonium salt during the reaction. Specific examples of the acid or acid anhydride used include nitric acid, hydrochloric acid, perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, sulfuryl chloride, boric acid, arsenic acid, arsenous acid, Pyroarsenic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus sulfide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrocyanic acid, chromic acid, anhydrous nitric acid, anhydrous sulfuric acid, Inorganic acidic compounds such as boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, silica gel, silica alumina, aluminum chloride, zinc chloride, formic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, Butyric acid, succinic acid, valeric acid, caproic acid, caprylic acid, naphthenic acid, methyl mercaptopropionate, malonic acid, glutaric acid, adipic acid, cyclohexanecarboxylic acid, thiodipropionic acid, dithiodi Lopionic acid acetic acid, maleic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, salicylic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic Acid, terephthalic acid, salicylic acid, benzylic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyrone anhydride Organic carboxylic acids such as merit acid, trimellitic anhydride, trifluoroacetic anhydride, mono, di and trimethyl phosphate, mono, di and triethyl phosphate, mono, di and triisobutyl phosphate, mono, di and tributyl phosphate, mono, di And trilauryl phosphate Acids and phosphorous acids in which these phosphate moieties are phosphites, organic phosphorus compounds such as dialkyldithiophosphoric acids represented by dimethyldithiophosphoric acid, phenol, catechol, t-butylcatechol, 2,6-di-t- Butyl cresol, 2,6-di-t-butylethylphenol, resorcin, hydroquinone, phloroglucin, pyrogallol, cresol, ethylphenol, butylphenol, nonylphenol, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetamide, methyl hydroxyphenylacetate Hydroxyethyl ethyl acetate, hydroxyphenethyl alcohol, hydroxyphenethylamine, hydroxybenzaldehyde, phenylphenol, bisphenol-A, , 2'-methylene-bis (4-methyl-6-t-butylphenol), bisphenol-F, bisphenol-S, α-naphthol, β-naphthol, aminophenol, chlorophenol, 2,4,6-trichlorophenol, etc. Phenols, methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, p-toluenesulfonic acid, ethylbenzenesulfonic acid, butylbenzenesulfonic acid , Dodecylbenzenesulfonic acid, p-phenolsulfonic acid, o-cresolsulfonic acid, metanilic acid, sulfanilic acid, 4B-acid, diaminostilbenesulfonic acid, biphenylsulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peri acid Laurent acid, sulfonic acids such as phenyl J acid, etc., and can be used in combination of some of these. Preferably, formic acid, acetic acid, peracetic acid, thioacetic acid, succinic acid, tartaric acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic acid, caprylic acid, naphthenic acid, methyl mercaptopropionate, malonic acid, glutaric acid, adipine Acid, cyclohexanecarboxylic acid, thiodipropionic acid, dithiodipropionic acid acetic acid, maleic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, salicylic acid, 2-methoxybenzoic acid, 3 -Methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, benzylic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, anhydrous Maleic acid, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, trime anhydride Organic carboxylic acids such as litnic acid and trifluoroacetic anhydride, more preferably acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, triflic anhydride Mellitic acid, an acid anhydride of trifluoroacetic anhydride, and most preferably acetic anhydride. The amount added is usually in the range of 0.001% to 10% by weight, preferably 0.01% to 5% by weight, based on the total amount of the reaction solution. When the addition amount is less than 0.001% by mass, the production of the polymer becomes remarkable and the reaction yield decreases, and when it exceeds 10% by mass, the yield may decrease remarkably. Specific examples of ammonium salts include ammonium chloride, ammonium bromide, ammonium iodide, ammonium formate, ammonium acetate, ammonium propionate, ammonium benzoate, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium phosphate, ammonium hydroxide, and the like. Is mentioned. More preferred are ammonium nitrate, ammonium sulfate, and ammonium chloride, and most preferred is ammonium nitrate.

It describes about the manufacturing method of the compound represented by Formula (5) from the compound represented by Formula (4).
The compound represented by Formula (5) is obtained by reaction of the compound represented by Formula (4) with an epihalohydrin compound. Examples of the epihalohydrin compound include epichlorohydrin and epibromohydrin, with epichlorohydrin being preferred.
When the epihalohydrin is reacted with the compound represented by the formula (4), a catalyst is preferably used. Examples of the catalyst include inorganic acid, organic acid, Lewis acid, silicic acid, boric acid, quaternary ammonium salt, inorganic base, organic base and the like. Preferred are organic acids, quaternary ammonium salts, and inorganic bases, and more preferred are quaternary ammonium salts and inorganic bases. Specific examples include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium acetate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium acetate, tetrahexylammonium. Examples include chloride, tetrahexylammonium bromide, tetrahexylammonium acetate, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium acetate, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide. Of these, sodium hydroxide, potassium hydroxide, and calcium hydroxide are preferred.

The amount of the catalyst added is not particularly limited as long as the reaction is allowed to proceed. However, it is preferably used in an amount of 0.00001 to 0.5 mol, more preferably 0.001 to 0.1 mol, relative to 1 mol of epihalohydrin. . If the amount is less than 0.00001 mol, the reaction does not proceed or becomes too slow, which is not preferable.
The proportion of the epihalohydrin and the compound represented by the formula (4) is not particularly limited as long as the reaction proceeds, but preferably the epihalohydrin to the thiol group (SH group) of the compound represented by the formula (4) The molar ratio is 0.3 to 4, more preferably 0.4 to 3, and still more preferably 0.5 to 2. If it is less than 0.3 or exceeds 4, the surplus of unreacted raw materials increases, which is not economically preferable.

It describes about the manufacturing method of the compound represented by Formula (6) from the compound represented by Formula (5). The compound represented by the formula (7) can be produced from the compound represented by the formula (3) by the same method.
The compound represented by the formula (6) is obtained by reacting the compound represented by the formula (5) with an alkali. Specific examples of the alkali include hydroxides of ammonia, alkali metals, and alkaline earth metals. And alkali metal and alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali metal and alkaline earth metal ammonium salts, and the like. These may be used as an aqueous solution. Sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate are preferable, and sodium hydroxide and potassium hydroxide are more preferable.
The amount of alkali to be used cannot be generally defined by the compound represented by the formula (5) as a raw material, but usually the alkali is 0.8 to 1 relative to the halogen equivalent in the compound represented by the formula (5). .2 equivalents, preferably 0.84 to 1.14 equivalents, more preferably 0.90 to 1.1 equivalents. When the amount of alkali is small or large, the yield decreases.

The solvent used in the reaction is not particularly limited and any solvent may be used, but preferably water, alcohols, ethers, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons. And the like are used. These may be used alone or in combination. Specific examples of alcohols include methanol, ethanol, propanol, isopropanol, etc. Specific examples of ethers include diethyl ether, tetrahydrofuran, dioxane, etc. Specific examples of ketones include methyl cellosolve. , Ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, acetone and the like, specific examples of aliphatic hydrocarbons include hexane, heptane, octane and the like, and specific examples of aromatic hydrocarbons include benzene , Toluene, xylene and the like. Specific examples of the halogenated hydrocarbons include dichloroethane, chloroform, chlorobenzene and the like. More preferred are water and alcohols, and specific examples thereof include water, methanol, propanol and isopropanol. Of these, water and methanol are preferred.
The amount of the solvent is not particularly limited, but is usually 5 to 1000 parts by weight, preferably 50 to 500 parts by weight, more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the compound represented by the formula (3). is there.
The reaction temperature is not particularly limited as long as the reaction is allowed to proceed, but is preferably −10 ° C. to 80 ° C., more preferably 0 ° C. to 50 ° C., and further preferably 0 ° C. to 30 ° C. The reaction time is not particularly limited, but is usually 20 hours or less. If it is less than −10 ° C., it is not preferable because the reaction does not proceed or becomes too slow.

It describes about the manufacturing method of the compound in which n and q of Formula (1) are represented by 0 from the compound represented by Formula (6). The compound represented by Formula (1) can also be manufactured from the compound represented by Formula (8) by the same method.
An episulfide compound represented by the formula (1) is obtained by reacting a compound represented by the formula (6) with a thiating agent such as thiourea or thiocyanate. Preferred thiating agents are thiurea, sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, and a particularly preferred compound is thiourea. As the thialating agent, the number of moles corresponding to the epoxy of the compound represented by formula (6), that is, the theoretical amount is used. If importance is attached to the reaction rate and purity, the theoretical amount to 2.5 times the theoretical amount. Use moles. The molar amount is preferably 1.3 times the theoretical amount to 2.0 times the theoretical amount, more preferably 1.5 times the theoretical amount to 2.0 times the theoretical amount.
The solvent is not particularly limited as long as it dissolves the chelating agent, the compound represented by the formula (6), and the episulfide compound represented by the formula (1), but specific examples include alcohols such as methanol and ethanol. , Ethers such as diethyl ether, tetrahydrofuran and dioxane, hydroxy ethers such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, aromatic hydrocarbons such as benzene and toluene, and halogenation such as dichloromethane, chloroform and chlorobenzene Examples include hydrocarbons and water. Alcohols, aromatic hydrocarbons, and water are preferable, and methanol and toluene are more preferable. These may be used alone or in combination.
The reaction temperature is not particularly limited as long as the reaction proceeds. Usually, the reaction is carried out at 10 ° C to 50 ° C. When the temperature is lower than 10 ° C., in addition to the decrease in the reaction rate, the thiating agent is insufficiently dissolved and the reaction does not proceed sufficiently. When the temperature exceeds 50 ° C., the formation of the polymer becomes remarkable.

It describes about the manufacturing method of the compound in which m and p of Formula (1) are 0, n and q are 1 from the compound represented by Formula (4).
A compound represented by the formula (4) and 3-mercapto-1,2-propylene sulfide are reacted with an oxidizing agent to obtain an episulfide compound represented by the formula (1). Preferred oxidizing agents are halogen, hydrogen peroxide, permanganate, and chromic acid, more preferably halogen and hydrogen peroxide, and particularly preferably iodine.
The solvent is not particularly limited as long as it dissolves the oxidizing agent, the compound represented by formula (4), and the episulfide compound represented by formula (1). Specific examples include alcohols such as methanol and ethanol. , Ethers such as diethyl ether, tetrahydrofuran and dioxane, hydroxy ethers such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, aromatic hydrocarbons such as benzene and toluene, halogenated carbonization such as dichloromethane, chloroform and chlorobenzene Examples include hydrogen and water. Alcohols, aromatic hydrocarbons, and water are preferable, and methanol and toluene are more preferable. These may be used alone or in combination.
The reaction temperature is not particularly limited as long as the reaction proceeds. Usually, the reaction is performed at −30 ° C. to 20 ° C. When the temperature is lower than −30 ° C., the reaction does not proceed sufficiently due to a decrease in the reaction rate, and when it exceeds 20 ° C., the reaction may proceed excessively.

In the composition for optical materials of the present invention, an episulfide compound represented by the formula (2) can be used as the polymerizable compound. Specific examples of the episulfide compound represented by the formula (2) include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane, 1,2 And episulfides such as -bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, and 1,4-bis (β-epithiopropylthio) butane. The episulfide compound represented by the formula (2) may be used alone or in combination of two or more.
Among them, preferred compounds are bis (β-epithiopropyl) sulfide (n = 0 in formula (2)) and bis (β-epithiopropyl) disulfide (m = 0 in formula (2), n = 1). The most preferred compound is bis (β-epithiopropyl) sulfide (n = 0 in the formula (2)).

The composition for optical materials of the present invention may contain a polythiol compound as a polymerizable compound in order to improve the color tone when the resulting resin is heated. The content of the polythiol compound is usually 1 to 25% by mass, preferably 2 to 25% by mass, particularly preferably 5 to 20% by mass, when the total amount of the composition for optical materials is 100% by mass. . When the content of the polythiol compound is less than 1% by mass, yellowing may occur during lens molding, and when it exceeds 25% by mass, the heat resistance may decrease. The polythiol compound used in the present invention may be used alone or in combination of two or more.
Specific examples thereof include methanedithiol, methanetrithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,4-dimer. Mercaptobutane, 1,6-dimercaptohexane, bis (2-mercaptoethyl) ether, bis (2-mercaptoethyl) sulfide, 1,2-bis (2-mercaptoethyloxy) ethane, 1,2-bis (2 -Mercaptoethylthio) ethane, 2,3-dimercapto-1-propanol, 1,3-dimercapto-2-propanol, 1,2,3-trimercaptopropane, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 2- (2-mercaptoethylthio) -1, Dimercaptopropane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, 4,8-dimercaptomethyl-1, 11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11- Dimercapto-3,6,9-trithiaundecane, 1,1,1-tris (mercaptomethyl) propane, tetrakis (mercaptomethyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopro Pionate), diethylene glycol bis (2-mercaptoacetate), die Lenglycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate), trimethylolpropane tristhioglycolate, Trimethylolpropane trismercaptopropionate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakismercaptopropionate, 1,2-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1, 3-bis (mercaptomethyl) cyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane 2,5-bis (2-mercaptoethylthiomethyl) -1,4-dithian, 2,5-dimercaptomethyl-1-thian, 2,5-dimercaptoethyl-1-thian, 2,5-di Mercaptomethylthiophene, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, 2,2-bis (4-mercaptophenyl) propane, bis (4-mercaptophenyl) ether, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) sulfone, bis (4-mercaptomethylpheny ) Methane, 2,2-bis (4-mercaptomethylphenyl) propane, bis (4-mercaptomethylphenyl) ether, bis (4-mercaptomethylphenyl) sulfide, 2,5-dimercapto-1,3,4-thiadiazole 3,4-thiophenedithiol, 1,1,3,3-tetrakis (mercaptomethylthio) propane and the like.
Among these, preferred specific examples are bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercapto). Methyl) benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-di Mercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 1,1,3,3 -Tetrakis (mercaptomethylthio) propane, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakis Thioglycolate, trimethylolpropane tristhioglycolate), and trimethylolpropane trismercaptopropionate, more preferably bis (2-mercaptoethyl) sulfide, 2,5-bis (2-mercaptomethyl)- 1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,3-bis (mercaptomethyl) benzene, pentaerythritol tetrakismercaptopropionate, and pentaerythritol tetrakisthioglycolate Particularly preferred compounds are bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

The composition for optical materials of the present invention may contain a polyisocyanate compound as a polymerizable compound in order to improve the strength of the resulting resin. The content of the polyisocyanate compound is usually 1 to 25% by mass, preferably 2 to 25% by mass, particularly preferably 5 to 20% by mass, when the total composition for optical materials is 100% by mass. is there. If the content of the polyisocyanate compound is less than 1% by mass, the strength may decrease, and if it exceeds 25% by mass, the color tone may deteriorate. The polyisocyanate compound used in the present invention may be used alone or in combination of two or more.
Specific examples thereof include diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate, 2,6-bis (isocyanatomethyl) decahydronaphthalene, lysine triisocyanate, tolylene diisocyanate, o-tolidine diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, 3- (2'-isocyanatocyclohexyl) propyl isocyanate, isopropylidenebis (cyclohexyl isocyanate) ), 2,2′-bis (4- Socyanate phenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 4,4 ′, 4 ″ -triisocyanate-2,5-dimethoxyphenylamine, 3,3′-dimethoxybenzidine-4, 4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diisocyanate biphenyl, 4,4'-diisocyanate-3,3'-dimethylbiphenyl, dicyclohexylmethane-4,4'- Diisocyanate, 1,1'-methylenebis (4-isocyanatebenzene), 1,1'-methylenebis (3-methyl-4-isocyanatebenzene), m-xylylene diisocyanate, p-xylylene diisocyanate, m-tetramethylxylylene diene Socyanate, p-tetramethylxylylene diisocyanate, 1,3-bis (2-isocyanate-2-propyl) benzene, 2,6-bis (isocyanatomethyl) naphthalene, 1,5-naphthalene diisocyanate, bis (isocyanatomethyl) tetrahydro Dicyclopentadiene, bis (isocyanatemethyl) dicyclopentadiene, bis (isocyanatemethyl) tetrahydrothiophene, bis (isocyanatemethyl) norbornene, bis (isocyanatemethyl) adamantane, thiodiethyldiisocyanate, thiodipropyldiisocyanate, thiodihexyldiisocyanate, bis [ (4-Isocyanatemethyl) phenyl] sulfide, 2,5-diisocyanate-1,4-dithiane, 2,5-diisocyanate Methyl-1,4-dithiane, 2,5-diisocyanate methyl thiophene, dithio diethyl diisocyanate, and the like dithio dipropyl diisocyanate.

However, the polyisocyanate compounds used in the present invention are not limited to these, and these may be used alone or in combination of two or more.
Of these, preferred examples are isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate. 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, bis (isocyanatemethyl) norbornene, and 2,5-diisocyanatomethyl-1,4-dithiane, among which preferable compounds Is isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, Is (isocyanatomethyl) cyclohexane, and m- xylylene diisocyanate, are particularly preferred compounds, isophorone diisocyanate, m- xylylene diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane.

Further, the ratio of the SH group in the polythiol compound to the NCO group of the polyisocyanate compound, that is, [the number of SH groups of the polythiol compound / the number of NCO groups of the polyisocyanate compound] (SH group / NCO group) is preferably 1.0 to 2. 5, more preferably 1.25 to 2.25, and still more preferably 1.5 to 2.0. If the above ratio is less than 1.0, it may be colored yellow at the time of lens molding, and if it exceeds 2.5, the heat resistance may be lowered.

The composition for optical materials of the present invention may contain sulfur as a polymerizable compound in order to improve the refractive index of the obtained resin. The content of sulfur is usually 0.1 to 15% by mass, preferably 0.2 to 10% by mass, particularly preferably 0.3% when the total composition for optical materials is 100% by mass. ~ 5% by mass. In the method for producing an optical material of the present invention, the compound represented by the formula (2) and sulfur may be partially polymerized in advance.
The shape of sulfur used in the present invention may be any shape. Specifically, the sulfur is finely divided sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur or the like, but preferably finely divided sulfur with fine particles.
The production method of sulfur used in the present invention may be any production method. Sulfur production methods include sublimation purification from natural sulfur ore, mining by melting sulfur buried underground, recovery methods using hydrogen sulfide obtained from oil and natural gas desulfurization processes, etc. Any method is acceptable.
The particle size of sulfur used in the present invention is preferably smaller than 10 mesh, that is, the sulfur is finer than 10 mesh. When the particle size of sulfur is larger than 10 mesh, it is difficult to completely dissolve sulfur. For this reason, an unfavorable reaction or the like may occur in the first step, resulting in a problem. The particle size of sulfur is more preferably smaller than 30 mesh, and most preferably smaller than 60 mesh.
The purity of sulfur used in the present invention is preferably 98% or more, more preferably 99.0% or more, still more preferably 99.5% or more, and most preferably 99.9% or more. When the purity of sulfur is 98% or more, the color tone of the obtained optical material is further improved as compared with the case where the purity is less than 98%.

When the optical material composition of the present invention is polymerized and cured to obtain an optical material, it is preferable to add a polymerization catalyst. The composition of the present invention may be a polymerization curable composition comprising a composition for optical materials and a polymerization catalyst. As the polymerization catalyst, amine, phosphine, onium salt and the like are used, and onium salts, particularly quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, and secondary iodonium salts are particularly preferable. Quaternary ammonium salts and quaternary phosphonium salts having good compatibility with the material composition are more preferable, and quaternary phosphonium salts are more preferable. More preferable polymerization catalysts include tetra-n-butylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, quaternary ammonium salts such as 1-n-dodecylpyridinium chloride, tetra-n-butylphosphonium bromide, tetra And quaternary phosphonium salts such as phenylphosphonium bromide. Of these, more preferred polymerization catalysts are tetra-n-butylammonium bromide, triethylbenzylammonium chloride, and tetra-n-butylphosphonium bromide.
The addition amount of the polymerization catalyst varies depending on the components of the composition, the mixing ratio and the polymerization curing method, but cannot be determined unconditionally. Usually, the total amount of the composition for optical materials is 100% by mass (amount not including the polymerization catalyst). To 0.0001 mass% to 10 mass%, preferably 0.001 mass% to 5 mass%, more preferably 0.01 mass% to 1 mass%, and most preferably 0.01 mass% to 0.001 mass%. 5% by mass. When the addition amount of the polymerization catalyst is more than 10% by mass, polymerization may occur rapidly. On the other hand, if the addition amount of the polymerization catalyst is less than 0.0001% by mass, the composition for optical materials may not be sufficiently cured and the heat resistance may be poor.

Further, when an optical material is produced by the production method of the present invention, it is possible to further improve the practicality of the resulting optical material by adding additives such as an ultraviolet absorber, a bluing agent, and a pigment to the optical material composition. Of course it is possible.
Preferred examples of the ultraviolet absorber are benzotriazole compounds, and particularly preferred compounds are 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di -Tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-methoxyphenyl) -2H-benzo Triazole, 2- (2-hydroxy-4-ethoxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-butoxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) ) -2H-benzotriazole, and 2- (2-hydroxy-5-t-octylph) Sulfonyl) is -2H- benzotriazole.
The added amount of these ultraviolet absorbers is usually 0.01 to 5% by mass with respect to 100% by mass in total of the composition for optical materials.

When the composition for optical material is polymerized and cured, a polymerization regulator can be added as necessary for the purpose of extending the pot life or dispersing the polymerization heat. Examples of the polymerization regulator include halides of Groups 13 to 16 in the long-term periodic table. Among these, preferred are halides of silicon, germanium, tin and antimony, and more preferred are chlorides of germanium, tin and antimony having an alkyl group. More preferred compounds are dibutyltin dichloride, butyltin trichloride, dioctyltin dichloride, octyltin trichloride, dibutyldichlorogermanium, butyltrichlorogermanium, diphenyldichlorogermanium, phenyltrichlorogermanium, and triphenylantimony dichloride, the most preferred compounds are Dibutyltin dichloride. The polymerization regulator may be used alone or in combination of two or more.
The addition amount of the polymerization regulator is 0.0001 to 5.0% by mass, preferably 0.0005 to 3.0% by mass, more preferably 100% by mass of the total composition for optical materials. Is 0.001 to 2.0 mass%. When the addition amount of the polymerization regulator is less than 0.0001% by mass, a sufficient pot life cannot be secured in the resulting optical material, and when the addition amount of the polymerization regulator is more than 5.0% by mass, The material composition may not be sufficiently cured, and the heat resistance of the obtained optical material may be reduced.

The optical material composition or the polymerization curable composition thus obtained is cast into a mold or the like and polymerized to obtain an optical material.
In casting the composition of the present invention, it is preferable from the viewpoint of improving the quality of the optical material of the present invention to remove impurities by filtering with a filter having a pore diameter of about 0.1 to 5 μm.
The polymerization of the composition of the present invention is usually performed as follows. That is, the curing time is usually 1 to 100 hours, and the curing temperature is usually −10 ° C. to 140 ° C. The polymerization is performed by a step of holding at a predetermined polymerization temperature for a predetermined time, a step of raising the temperature from 0.1 ° C. to 100 ° C./h, a step of lowering the temperature by 0.1 ° C. to 100 ° C./h, or these steps. Do it in combination.
In addition, after the curing is completed, annealing the obtained optical material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing the distortion of the optical material of the present invention. Further, the obtained optical material may be subjected to a surface treatment such as dyeing, hard coating, impact resistant coating, antireflection or imparting antifogging properties as necessary.
The optical material of the present invention can be suitably used as an optical lens. Optical lenses manufactured using the composition of the present invention are excellent in stability, hue, light resistance, and transparency, and thus, conventionally, expensive high refractive index glass lenses such as telescopes, binoculars, and television projectors have been used. It can be used in various fields and is extremely useful. If necessary, it is preferably used in the form of an aspheric lens. Since an aspherical lens can substantially eliminate spherical aberration with a single lens, there is no need to remove spherical aberration by combining a plurality of spherical lenses, which reduces weight and reduces production costs. It becomes possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.

Hereinafter, although the content of the present invention will be described with reference to examples and comparative examples, the present invention is not limited to the following examples.
1. Evaluation Method of Dyeability After the optical material was immersed in a dyeing bath having the following composition at 90 ° C. for 30 minutes, the total light transmittance was measured. The value calculated from the measured value by the following formula was defined as dyeability.
Dyeing property = 100−total light transmittance (%)
Dye bath composition:
Seiko Plax Diamond Coat Brown D0.2% by weight
Seiko Plax dyeing aid 0.3% by weight
Benzyl alcohol 2.0% by weight
A dyeing property of 70 or more was designated as A, 55 or more and less than 70 as B, 40 or more and less than 55 as C, and D as less than 40. A, B, and C are acceptable levels.
2. Method for evaluating releasability 100 -10D lenses were produced by the method described in the examples, and the releasability from the mold after polymerization and curing was evaluated. A with no lens chipping was designated as A, 1 or 2 was designated as B, and 3 or more was designated as C. A and B are acceptable levels.
3. Evaluation method of peeling: 100 -10D lenses were prepared by the method described in the examples, and the lens after polymerization curing was observed with a mercury lamp, and peeling was evaluated from the number of occurrences of surface accuracy defects on the lens surface. . A case where no lens peeling occurred was designated as A, 1 or 2 pieces were designated as B, and 3 or more pieces were designated as C. A and B are acceptable levels.

Synthesis Example 185 g (2.0 mol) of epichlorohydrin, 30 g of water, 5 g of methanol, and 1.5 g of 32% aqueous sodium hydroxide solution were placed in a 3 L flask, and 35 g (1.0 mol) of hydrogen sulfide was added at a liquid temperature of 5 to 15 ° C. while stirring. The mixture was blown in while maintaining bis (3-chloro-2-hydroxypropyl) sulfide (210 g, 0.96 mol).
Thereafter, 750 ml of toluene, 750 ml of methanol, 0.3 g of acetic anhydride and 350 g of thiourea were added and reacted at 40 ° C. for 10 hours. After completion of the reaction, water was added for washing, and the resulting organic layer was washed with 10% sulfuric acid and then with water, the solvent was distilled off, and then purified with a column to obtain 1,7-dimercapto-2,6-dihydroxy-4. -139 g (0.65 mol) of thiaheptane was obtained.

Example 1
19.5 g (0.2 mol) of epichlorohydrin, 30 g of water, 5 g of methanol, and 0.2 g of 32% aqueous sodium hydroxide solution were placed in a 1 L flask, and 1,7-dimercapto obtained in the above synthesis example while stirring. -2,6-dihydroxy-4-thiaheptane (21.4 g, 0.1 mol) was added dropwise while maintaining the liquid temperature at 5 to 15 ° C. to give bis- (2,6-dihydroxy-7-chloro-4-thiaheptyl) sulfide. Obtained.
After adding 100 g of water, 25 g of a 32% aqueous sodium hydroxide solution was added dropwise while maintaining the temperature at 0 to 10 ° C. Thereafter, 100 g of methyl isobutyl ketone was added for extraction, and the resulting organic layer was washed with 1% acetic acid and then with water, the solvent was distilled off, and then purified with a column to obtain bis- (2-hydroxy-6,7 -Epoxy-4-thiaheptyl) sulfide (20 g, 0.06 mol) was obtained.
Thereafter, 200 ml of toluene, 200 ml of methanol, 0.2 g of acetic anhydride, and 19 g of thiourea were added and reacted at 40 ° C. for 10 hours. After completion of the reaction, water was added for washing, and the resulting organic layer was washed with 10% sulfuric acid and then with water, the solvent was distilled off, and then purified with a column, and bis- (2- 16 g (0.04 mol) of hydroxy-6,7-epithio-4-thiaheptyl) sulfide was obtained.

¹ H-NMR (CDCl ₃ ): 2.0 ppm (2H), 2.2-2.7 ppm (18H), 3.8 ppm (2H)
¹³ C-NMR (CDCl ₃ ): 26 ppm (2C), 33 ppm (4C), 44 ppm (2C), 45 ppm (2C), 77 ppm (2C)

Example 2
1,7-dimercapto-2,6-dihydroxy-4-thiaheptane 15 g (0.07 mol), 3-mercapto-1,2-propylene sulfide 15 g (0.14 mol) obtained in the synthesis example, toluene 100 mL, methanol 100 mL And 23.2 g (0.14 mol) of potassium iodide were added to the 1 L flask. While stirring while maintaining the internal temperature at −20 ° C., 35.6 g (0.14 mol) of iodine solid was charged in portions and aged for 4 hours. After completion of the reaction, 100 mL of toluene was added, the organic layer was taken out, filtered, and washed with brine, 1% sulfuric acid, and brine. The obtained organic layer was dehydrated over anhydrous magnesium sulfate and filtered, and the solvent of the obtained filtrate was distilled off. Thereafter, purification with a column yielded 11.4 g (0.03 mol) of bis- (2-hydroxy-7,8-epithio-4,5-dithiaoctyl) sulfide represented by the following structural formula.

¹ H-NMR (CDCl ₃ ): 2.0 ppm (2H), 2.2-3.0 ppm (18H), 3.8 ppm (2H)
¹³ C-NMR (CDCl ₃ ): 24 ppm (2C), 33 ppm (4C), 45 ppm (2C), 46 ppm (2C), 78 ppm (2C)

Example 3
As the episulfide compound represented by the above formula (2), bis (β-epithiopropyl) sulfide (hereinafter referred to as “b-1 compound”) was obtained in Example 1 as the episulfide compound represented by the above formula (1). The obtained bis- (2-hydroxy-6,7-epithio-4-thiaheptyl) -sulfide (hereinafter referred to as “a-1 compound”) was added to obtain a composition containing 0.001% by mass of the a-1 compound. It was. 79.0 parts by mass of the obtained composition, 0.5 part by mass of sulfur, and 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H- Benzotriazol-2-yl) phenol] (trade name Biosorb 583, manufactured by Kyodo Yakuhin Co., Ltd.) 0.9 parts by mass was mixed at 30 ° C. for 1 hour to obtain a first solution. Thereafter, the first liquid was cooled to 10 ° C. After thoroughly mixing 6.6 parts by mass of pentaerythritol tetrakismercaptopropionate, 0.08 parts by mass of tetra-n-butylphosphonium bromide, and 0.01 parts by mass of dibutyltin dichloride at a mixing temperature of 20 ° C. and uniforming, In addition to the first liquid, the mixture was stirred for 30 minutes at a mixing temperature of 15 ° C. to obtain a second liquid that was uniform. A release agent Zelec UN (manufactured by Stepan) 0.01 parts by mass and m-xylylene diisocyanate 7.1 parts by mass were mixed well at 20 ° C., and the mixture was homogenized and added to the second liquid. The mixture was degassed and stirred for 2.5 hours at a reaction temperature of 15 ° C. and a vacuum of 0.27 kPa, and the mixture was reacted to obtain a reaction mixture. 6.8 parts by mass of bis (2-mercaptoethyl) sulfide was added to the reaction mixture in the reaction flask, degassed and stirred at 15 ° C. for 30 minutes and at a vacuum of 0.27 kPa to obtain a composition for optical materials. Obtained. The obtained composition for optical material was poured into a mold composed of two glass plates and a tape, held at 30 ° C. for 30 hours, heated to 100 ° C. over 10 hours, and finally at 100 ° C. for 1 hour. It was held for a time and polymerized and cured. After cooling, the mold was released from the mold and annealed at 110 ° C. for 60 minutes. Table 1 summarizes the evaluation results of releasability from the mold, peeling, and dyeability.

Examples 4 to 9, Comparative Example 1
An optical material was obtained according to Example 3 except for the addition amount of the a-1 compound (compound of formula (1)). The evaluation results are summarized in Table 1.

Example 10
As the episulfide compound represented by the above formula (2), bis (β-epithiopropyl) disulfide (hereinafter referred to as “b-2 compound”) was obtained as the episulfide compound represented by the above formula (1) in Example 2. And a bis- (2-hydroxy-7,8-epithio-4,5-dithiaoctyl) -sulfide (hereinafter referred to as “a-2 compound”) added, and a composition containing 0.001% by mass of the a-2 compound Got. 79.0 parts by mass of the obtained composition, 0.5 part by mass of sulfur, and 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H- Benzotriazol-2-yl) phenol] (trade name Biosorb 583, manufactured by Kyodo Yakuhin Co., Ltd.) 0.9 parts by mass was mixed at 30 ° C. for 1 hour to obtain a first solution. Thereafter, the first liquid was cooled to 10 ° C. After thoroughly mixing 6.6 parts by mass of pentaerythritol tetrakismercaptopropionate, 0.08 parts by mass of tetra-n-butylphosphonium bromide, and 0.01 parts by mass of dibutyltin dichloride at a mixing temperature of 20 ° C. and uniforming, In addition to the first liquid, the mixture was stirred for 30 minutes at a mixing temperature of 15 ° C. to obtain a second liquid that was uniform. A release agent Zelec UN (manufactured by Stepan) 0.01 parts by mass and m-xylylene diisocyanate 7.1 parts by mass were mixed well at 20 ° C., and the mixture was homogenized and added to the second liquid. The mixture was degassed and stirred for 2.5 hours at a reaction temperature of 15 ° C. and a vacuum of 0.27 kPa, and the mixture was reacted to obtain a reaction mixture. 6.8 parts by mass of bis (2-mercaptoethyl) sulfide was added to the reaction mixture in the reaction flask, degassed and stirred at 15 ° C. for 30 minutes and at a vacuum of 0.27 kPa to obtain a composition for optical materials. Obtained. The obtained composition for optical material was poured into a mold composed of two glass plates and a tape, held at 30 ° C. for 30 hours, heated to 100 ° C. over 10 hours, and finally at 100 ° C. for 1 hour. It was held for a time and polymerized and cured. After cooling, the mold was released from the mold and annealed at 110 ° C. for 60 minutes. Table 1 summarizes the evaluation of releasability, peeling, and dyeability from the mold.

Examples 11 to 16, Comparative Example 2
An optical material was obtained according to Example 10 except for the addition amount of the a-2 compound (compound of formula (1)). The evaluation results are summarized in Table 1.

As can be seen from Table 1, Examples 3 to 8 and 10 to 15 were evaluated to pass levels in all of peeling, releasability, and dyeability. On the other hand, Examples 9 and 16 were good in peeling and dyeing properties, but were not good in releasability. Comparative Examples 1 and 2 that do not contain the episulfide compound represented by the formula (1) had poor release properties but poor evaluation of peeling and dyeability.

Claims

An episulfide compound represented by the following formula (1).

(In the formula, m and p are integers of 0 to 4, and n and q are integers of 0 to 2.)
The composition for optical materials containing the episulfide compound represented by Formula (1) of Claim 1 and the episulfide compound represented by following formula (2).

(In the formula, m represents an integer of 0 to 4, and n represents an integer of 0 to 2.)
The composition for optical materials according to claim 2, wherein the content of the episulfide compound represented by the formula (1) is 0.001 to 5.0 mass%.
The composition for optical materials according to claim 2 or 3, wherein the content of the episulfide compound represented by the formula (2) is 40 to 99.999 mass%.
Furthermore, the composition for optical materials in any one of Claim 2 to 4 containing a polythiol.
The composition for optical materials according to any one of claims 2 to 5, further comprising sulfur.
Furthermore, the composition for optical materials of Claim 5 or 6 containing polyisocyanate.
A polymerization curable composition comprising the optical material composition according to any one of claims 2 to 7 and 0.0001 mass% to 10 mass% of a polymerization catalyst based on a total amount of the optical material composition.
An optical material obtained by curing the composition for an optical material according to any one of claims 2 to 7 or the polymerization curable composition according to claim 8.
An optical lens comprising the optical material according to claim 9.
A method for producing an optical material, comprising a step of adding 0.0001% by mass to 10% by mass of a polymerization catalyst with respect to the total amount of the composition for an optical material according to any one of claims 2 to 7, followed by polymerization and curing.
The method for producing an optical material according to claim 11, wherein the episulfide compound represented by the formula (2) and sulfur are partially polymerized in advance and then polymerized and cured.